Improvement in reducing metallic oxides and in refining the metal resulting therefrom



UNITED. STATES PATENT OFFICE.

JACOB Runen, or r1TTsBUnc,' PENNSYLVANIA.

mpnovrnruimnrbucmc maniac oxlnrs'mo ,mv mal-mme THE .METAL RESULTING nznrmon.

Speciilcation' forming part of Letters PiatentNo. $1,969, dated September 1l, 1866. I

lo -all whom it may l.

lBe it known thatI, JAooB Runen, of the city of ittsburg, in the county-of Allegheny und State of Pennsyls'ana, have invented anew and useful Improvement in theReduong of Metallic Oxides, and the Refining ofthe Metal resulting therefrom.; and [do hereby declare that the following is a full, clean-'and exactdes'cription thereof, reference being-had to the accompanying drawings,formiug part of thi'sspecilication, which illustrate the appa,

ratus employed in the process, and in which- Figure 1 isa plan or top view of my limproved apparatus. Fig. 2 is a side elevationthereof. Figr is a vertical section through the cupola and reducing-chamber. Fig. 4'rep resents the tanks used for holding'the ,water and hydrocarbon fluid used in my improvedent of 'the-United States were granted to me' for an improved mode of reducin'gmetallic oxides, iu which, after the metallic oxide or ore is melted in a cupola and run intoa de i tached chamber orreducer, it isideoxidized by theapplicatiou of a hydrocarbouineither a liquider-gaseous form.

' lhe invention which I am about'todescrbe in this specification is an improvement outhe process` forming, the subjectmatter of my formerpatent; and it consists in fusing the'ore or metallic oxide to be reduced in a' cupola, with or without carbonaceousfuel, and'by the aid of a blast of atmospheric air,*and running the melted ore, before it is reduced lto ametallic state, into a reducing-chamber placed uu-` der the cupola, and reducing the melted vorein'such'chamber below the influence Aofthe at: mospheric blast by' meansof a compound or' mixture of hydrogen and carbon', by which the metal is also reiinedand-puriiied.-

metal; also,'in the' construction-and application pf apparatus .employed for the described, and .the mode of using the waste vheat resnlting'from the chemical reduction 0f the metallic oxides for the melting of the ore previous .to4 its reduction.

'My improved process 1s applicable to they rednctionaud. refining of the oxides of 'various metals, and the removal of sulphur, phosphorusfandfother impurities therefrom; but, forthe sake of perspicuity, I shall` confine my description tothe application 'of my invention in themanufactureofiron in its various forms of. malleable iron, semi-steel, cast-steel, and crude 'or veast iron.

One ofthe important'features of my improvement, in its' application to the manufacture of. iron, is theremoval of'sulphur Vand phosphorus, which results from the use of my invention. Manyof the best ores of iron contain a large amount ot' sulphur, which, having a greater vaiiinity foriron than for -either oxygen or carbon, is extremelydiicult to remove and When'these 'ores are' smeltedv in a blastfurnace fwit-h -coal or coke, which'likewisecontain sulphur, they take up an additional quantity, and the resulting metal becomes very red short.` Phosphorus, in the condition of'phosphate'of lime, or of phosphoric acid, is also found Vinsonne valuable ores ofiron, and is so -very diiicult-toremove that it is seldom attempted. It is' sometimes done, as in the case' of the magnetic iron ores of Lake'Champlain,

vby mechanical means, `-aiter 'theore-has been crushed by stamps," as this ore is very rich;A

.and,1when freed from' phosphorus, peculiarly adaptedfor making the best lbrands of cast--` steel; whereas, if not thus puried, it would vproduce'irontoo `cold-'short for' that purpose.

By the use of hydrogen in the fusion' and ,chemical reduction of ores containing sulphur or phosphorus, these impurities-ilaving a greater aiiinity for the hydrogen'unitewith it and leave thegiron neutrali-that is, neither redshort nor cold-short. 'The hydrogen forms no chemical combination with the iron, but

passes oli' as sulphureted or phosph uretedhyd-regen, while the iron thus puriedlismore My invention also" consists in' the compound ofhydrogeu, carbon, and oxygen employed iu' reducing the o're and refiningthe resulting- The advantages of-my Aimproved process overthe ordinary mode of smelting iron in a blast-furnace, by which the iron is highlycarbonized, and then decarbonizing it by puddling or boiling, or by the pneumatic process pleated.

My improvement is designed to edect the production of malleable or Wrought iron, steel or castiron from the ore, in the first instance, by fusing the ore iu a cupola or other furnace, without thereby reducing it-to its base, and then deoxidizing the liquid ore by means of hydrogen or carbon, or a mixture of those ele. ments, these deoxidizing agents being exhibited in such quantities as to produce the desired results-thatis to say, the hydrogen unitesA with the oxygen ot' the ore and` ,is burned, and also unites with and carries olf the sulphur or phosphorus, and the carbon, uniting with the oxygen of the ore, produces t vivid combustionund a high degree of heat,

(which is utilized in melting,r the ore in the cupola above,) no more carbon being employed than is necessary for that purpose, so that the iron is not carbonized, unless it is desired to produce semi-steel, cast steel, or cast-iron, in'

which case the requisite percentage of carbon is supplemented.

inthe practical application of my invention the vapor ot petroleum, or thev liquid itself, may be used as described in my former patent; or hydrogen may be obtaiuedfrom water, steam, petroleum, or other "substances, or carbureted hydrogen in the shape of'coal -gas may be employed. The carbon employed in the process may be used in a liquid, gaseous, or solid form, as may be most convenient, and may be extracted from coal,- petroleum, or therwise, or .used in the shape .of pnlverized coal, coke, or charcoal. The apparatus used may be modified to -conform to these 'various conditions, so that I do not Wishto limit myself to the specific details herein described.

'.lo enable others skilled in the art to make u'seof my invention and apply the 'process to the manufacture of nietals from their oxides, I will proceed `to describe the construction and operation of 'my apparatus. ln the drawings, A is the cupola in which the ore is melted. It is furnished with an annular blast-pipe, a, having tuyeres b, by which a blast ot' atmospheric air is introduced at or near the base of the cupola, for the purpose of supplying Asutiicient oxygen to keep up the heat necessary to fuse the ore.

The bottom of the cupola is not closed, as is usual, by a plate, but is loft open, so as to conilnunioate with the month of the reducingchamber B, placed directly below it, so that the ore, as` it is melted, may run' down immedi- -ately into the reducing-chamber below the. inilucnce of the atmospheric blast.

The cupola thus constructed andv arranged differs from a blast-furnace in this respect, that `tho blastfurnace is made withboshes tapering" downward so rapidly as to form a support for the charge of ore and fuel in the furnace and hold the burden up from the hearth until it is thoroughly deoxidized and charged with carbon, while my cupola is made with sides only slightly inclined, so as to allow the ore to pass down rapidly as soon as it is fused, and with- ?)ut ligeing deoxidized, into the redncingcham- The result of this difference of construction is, that in the blast-furnace the ore is deoxidized before. it is melted, and is in a metallic state before it runs down below the blast-line a: a' into. the hearth, 'while 'in my improved reducing-furnace the ore is only fused orliqueied in :the cupola above the blastfline a: a: and passes down below that line, as an oxide, into the .reducingrhambea where it is oxidized and reduced toa metallic state below the iny iluen'ce of the atmospheric blast.

In ,the blast-furnace the metal is wasted by oxidation while passing from the boshes through the blast, and forms black ciuder', the carbony in the metal being burned out, thus forming white iron instead of good grey pig,

My cupola is lined with iirebrick or other refractory substance which willresistthe action of the heat necessaryto fuse'the ore.

,The reducing-chamber B is a shallow cylindrical pot, made of wroughtiron, supported by a frame of castiron. 'It is lined with such material as will resist the heat and chemical action of reducing and refining, which may be varied according to the chemical composition of the orc under treatment. Thus, if the iron ore contains little or no silica` or alumina, (as the Edwards iron ore of Lake Superior,) pure lime or oxide of calcium may be used for lining the reducing-chamber, whilewith ores of other metals the lining may be pure alumina.

The reducing-chamber 'B has a shaft, c, at one side, placed at its upper edge, by means of which it is supported on pillow-blocks, in suitable bearings, and is'adjusted so as to fit closely up to the base-platedo one side ofthe cupola. By this shaft c the reducing-chamber B is pivoted so that it mayswingaway from the bottom ot' the cupola, as shown in Fig. 3, in

order to give free access to it, aswell-as tol the cupola, for the necessary repairs.

When iu use the foreplate c of the reducing, chamber is raised up, the shaft c turning in its bearings, until the foreplate e restsl against the under side ofthe base-plate d of the cupola, where it is fastened'bya latch, f, and thus held in place, with the open month of the reducingchamber coinciding with the open bottom of the cupola.

The shaft c is hollow from one end to the point whereit intersects the passage ,'formcd on the outside of the reducing-chamber l5. This passage i leads from the cavity c' of the shaft c downward to the cell g, a small cha-my ber formed under the bottom of the reducing chamber B, and cast in one piece with it.`

The bottom of the cell g is hermetically closed by a cap-plate, h, fastened on. by screws.

means of'one ormoret 'i struction.

I piece of gaspipe or other metallic tube, k, with ailanged head is embedded in the tuyere` while it is in a plastic condition, with the. tubular 'end 'projecting below the tuyere,'on which end screwthreads are cut, andY the tube 4k is then screwed into the casting between the reducing"-A chamber B and cell g, as shown in the drawings, an@ thus held in place. l

The diameter of the bore of the tuyere4 will be greater or less according to the capacity of the reducing-chamber and the character of the deoxidizing. agent employed in the process. 1f thisbe'in a liquid condition a`single tuyere of one-fourth inch diameter will ordinarily suflice, as the liquid expands enormously when it passes into a gaseouscondition on entering the molten mass in the reducer; but it' lthe reducing agent be' a gaseousbody the tuyeres should be increased in number, and.

' may be constructed as described in my former i patent before referred to.

The hollow'end of the shaft cis closed by a cap, to which is attachedone extremity ofthe pipe m, which .passes over the two tanks() and D, and has branches nu', which enter the `top of the closed tanks C and D, respectively, Through the pipes n n m the liquid contents of the tanks C D l'are forced into the cavity of the shaft' c,'a1d the/nce into the cell 'g, and.

grough the tuyere l into thereducing-cham- RB'. 1'- The tanks C and D holdthe deoxidizing agents, and a similar tank, E, contains water. From the top of the water-tank E astcam-pipe, p, leads `to a steam-generator. The pipes n and 'n' are each furnished with a registering-meter, F, to indicate the amount of gaseous or liquid reducing agentpassing through them. They have also cocks or valves o to regulate the flow.

The pipe m does not enter the -water-tank E, but vthe ,threetanks C, D,'and'E are connectcd togetherl Vunderneath by the pipe q, which opens into the bottom of each tank. The tanks maybe made of anyconvenient size, of ordina-ry boiler-ron,.onefourth of an inch thick, and with heads three-eighths of an inch thick.

For a reducing-chambercapable of making ilve tons of metal per hour, the tanks C and D should-have a capacity ot' not less than ten ybarrels each.

somewhat'flarg as it isdesigned tosupply e' water-tank E should be the requisite p i ure to the liuuid 'contents of the Atwo tanks (J l v'.lh blast -of atmospheric air is supplied -to the cupola by means of a blast-pipe, G r, which communicates with the two upright tubes H H, which also. serve as two ofthe supports of the cupola. The blast is conducted from the top of the tubes H H t'o the annular blastpipe a by means of the connecting-trunks I I.

Having thus described the construction of my improved apparatus, I will proceed'to explain the. mannerin which the operation is performed.

The process which I employ depends on the same general principles as that which is .de--

scribed iu my former patent of June 19, 1866. Instead of smelting the ore with carbon in the process ofdeoxidation, and thereby not only reducing it .to a metallic state, but saturating it with carbon, as' a iirst operation, and then reversing the process'and decarbonizing the.

i metal by forcing oxygen over or through it, I

propose to manufacture malleable iron, semi.

steel, cast-stcel, br cast-iron fromthe ore at one operation, by irstmelting theoxide or ore of iron with suiiicient air and carbon to melt without deoxidizing it, and then, during the same'process, to treat the melted oxide of iron with carbon or hydrogen, or a mixture of carbon and hydrogen, in` a receptacle placed below or beyond the reach of the atmospheric blast, until the oxygen is removed, when the.'

product will be malleable iron; or to continue `the 'supply of carbon until such4 percentage may be taken up by the melted metal as will yield the product desired, whether semi-steel, cast-steel, or cast-iron. y

The cupolaA. being. charged witli the iron ore, (oxide of iron,) and a suiicient amount of coke to create the necessary heat, and such purifying and iiuxing ingredients as may be desirable, the furnace is lighted and the blast applied. The ore, as itlnelts, drops downward into the reducing-chamber B, through the open bottom of the cupola, passing below the blastline aux, 'and -therefore ont of the influence of the blast, in the condition of a melted oxide.4 In, this ,colldition, beingnaturally combined ;with oxygen, (asan ore of iron,) the atmos'f phericblast has no effect to oxidize it any further, and there being no excess of carbon inthe cupola beyond the amount requisite for fuel, the ore is not either deoxidized or carbureted. .Asjthe liquid oxide of iron accumulates inthe reducing-chamber jB it floats the coke upon itssurface.

The tank C is lledwith benznole, or other liquidhydrocarbon', to be'used in reducing thc melted oxide toits base; the tank D with petroleuni-tar, or other vehicle of carbon, which is employed after 'thereduction of the oxide to add the requiredpercentage of carbon 'in the formation of steel or t-iron and the tank E with'water.

Just before the ore melts andrruns into the reducing-chamber, the valve o to the steampipe p 1s opened, and steam is Ylet intothe water-tank: 2E; which, pressing upon. the sur'- face of the water', forces'jit out through the pipe g, causing it .to enter thebottom of the tank C, butfn'ot into the tank D, which is 4 r om shut ou oy a cock. The pressure thus applied to the contents of the tank C forces ont the benzole or light hydrocarbon through thepipes um, and causes it to enterthe hollow' shaft c,- and'pass through the passage i and tuyerepl into the'reducing-chamber B. The water from the tank E, being heavier than tli'e benzole, remains in' the bottom of the tank O, displacing and forcing outthefbenzolc, which rushes with great force through the contracted aperture ofthe tuyere liuto vthe mass'of melted ore in the reducing-chamber B. The degree of foree'thus'appliedis regulated atpleasure by the admission of, steam through the vulve 0in the pipe p. f

The liquid light hydrocarbon thus injected .into the mass of melted ore expands with great force, producing great disturbance of the particles of molten orc, and causing an. intimate mixture therewith ofthe hydrogen and carbon.

The hydrogenrapidly unites with the oxygen of the ore,- formng water.(H0) or steam; and .the carbon, uniting with the oxygen and forming carbonic acid, (002,) thus e'ectnally deA oxiflizes the -orewithout carbureting iti. Thehydrogen also unites with the-sulphur and phosphorus in the ore, carrying olf these impurities where they exist. j

The union of the carbon and hydrogen with. vthe oxygen of the ore produces vivid combus- .tion 4and high heat, and the heat andjlame thus Vproduced pass up into the cupola,'and obviate the l necessity of using' other fuel to melt the cre contained therein, enabling the amount of coke employed for that purpose to bereduced to a very small quantity.

This operation is continued until the oxygen is all expelled from "the-ore, which is thereby reduced to a-mctallic state. .If theprocess be suspended at the point of complete deoxidation, the product will be malleable iron, .which muy-be run' out of tlie reducer-through the tap-hole r into r`suitable molds. The amount of light hydrocarbon used in the' operation of.

purpose, containing petroleum-tar, or other4 substance rich in carbon. The connection between the tank G containing the light hydrocarbon and the inducing-chamber- B having been closed when the reduction is. effected, the cock or valve o', connecting the top of the tank D with the reducing-chamber B is opened, when the pressure of water from the tank F, produced as before described, forces the heavy, carbon into the melted metal. As soon as the requisite percentage of carbon is taken up by l the 'metal the valve is closed and the operation-,of carbureting the metal is complete.l

The operation thus described maybe carried on continually, the-cupola being charged afresh as soon as'the contents ofthe reducer resulting from the'irst charge are removed. The ore will begin to melt in about twenty minutes from the'time the charge is putin, and the operation will bectnnpleted in from one to two hours, depending on the quantity of ore used. If, however, itis' desired to make the operation uninterlnittent or continuous, it. may be readily accomplished by a' slight modification in .the construction of the furnace, as 'siown in Fig. 5, in which there are two reducing4chambers, B andB', placed one on each side of the cupola, instead of vertically under. it. In this case the contents of the cupola rest on the bottom plate, and the melted ore is run through channels c c into the xeducers, first into the one and then -into the other, alter 'nately. Whenone reducer is filled with melted ore, the supply isstopped and turned into the other,'so that while one'reducerlis being filled the contents-of the other are being reduced by the application of the stream of hydrocarbon. Thus the process may bekept up without in termission. l

After the melted ore in the reducngcham ber has been thoroughly deoxidized, and, if desired, carbonized up to the desired point,-it maybe refined .by the use of la compound, which I call hydrelaion, or. hydroline,.being a mechanical compound or mixture of hydrogen, carbon, and oxygen, inl the proportions in which they will combine chemically. This mixture, the nature of which I shall particularly explain, is forced .through the melted metal in the reducing-chamber by means of tanks, such as before described. As soon as it enters themelted mass,- the elements composing the hydroline form animmediate. chemgive' out au intense heat, .which is communicated to the metal, and at the same time` cause it to boil violently.. By this means the metal is rened,and whatever sulphur or phophorns may yet remain is carried olf.

-Hydrelaion or hydroline, the mixture of which I use for refining the metal, is composed of carbon-oil or petroleum,- or other ci', and water, in the proportion of one atom of water to one of oil, orin such relative proportions depending ou the kind of oil employed) as wil produce tlie chemical equivalents ot' By means of this combination I provide a compound which containsin itself the elements required for combustion, without decomposing or wasting the metal, in the presence of which it isv chemically combined.

Hydroline may be procured by mixing water .and petroleum in a vessel and agitating it by pearance, when it will remain in mechanical ical union in 'a gaseous state,- and in so doingI water andthe oil used, supposed to.be ILOG.

mechanical means until it assumes a soapy apit may be made for immediate useby mixing the vapor of petroleum or coal-gas with steam, but I prefer the use of liquid` hydroline, as more convenient and eicient than the gaseous mixture, and -it will -be found more easy to mix the oil and water in the exact proportion desired, if they are in a liquid state.

lInstead of using steam in connection with the water-tank E for forcing the contents of the tanks C and D into the reducing-chamber, the force of a head of water, asfrom the reservoir of'a Waterworks, may be used when it is convenient to do so. The use of the watertank E,with the pressure of either steam or water, is much more efficient 'and economical than the ordinary cumbersome and expensive blowing-cylinders 5- and with live steam, any' required degree of pressure can be readily at tained and easily controlled.

The steam mightbe applied directly to the top of the oil, &c., in the tanks C and D, without the use of the water-tank E, but it would vaporize the hydrocarbons, which is not desirable.; besides, the steam would condense and settle at the bottom of the tank, and the water would be forced into thereducingchamber with the oil, &c.

What I claim as my invention, and desire to secure by Letters Patent, is

1. The manufacture of lironor other metals from their ores in a furnace, in which the ore, having been fused with the aid of' a blast of atmospheric air,.isthen reduced to its base with a hydrocarbon.

2. The process of fusing iron ores and other ymetallic oxides by the aid of a blast of atmospheric air in a furnace, and the waste heat v from the reducing-chamber, withoutthe use ofl other fuel, or with4 so little fuel .as not to deoxidze the ore in melting, and running ythe melted ore immediately into a receptacle below theiniluence of the atmospheric blast, in which it is deoxidized by the injection of any hydrocarbon into the molten mass, in the manner substantially as hereinbefore described.

3. The use -of an atmospheric blast for fusing metallic oxides, in combination with the use of hydrogen -or carbon or a hydrocarbon for thereduction of. the melted oxide to its' metallic base, substantially as' hereinbefore described.-

4. The use4 of the compound of water or.

steam and oil in a liquid or vaporous condi: tion, in the proportions hereinbefbre'described, as a new material for the refining of melted metal.v

5. Combining with a cupola or melting furnace one or more reducing-chambers, placed,

for the reception of the melted ore, below the point at which the atmospheric blast is introduced into the furnace, for the purpose of running the melted ore directlyfrom the furnace into a reducing-chamber, inwhich it may be dexidized, carbonized, and refined, away from the influence of the atmospheric blast,

substantially as hereinbefore described.

6. Connecting the reducing chamber `or chambers to the bottom of a cupola or meltin`g furnace'by a hingeorpivot, so that they maybe swungaway from thefu'rnace without :impairingtheir connection with the vessel .containing the reducing agent.

7. The use of the hollow' shaft c, in combination with the reducing-chamber B and connecting-passage t', for the purpose of hanging the reducer to the cupola, and allowing of the introduction into the reducing-chamber of the liquid or gaseous agents for the reduction of metallic oxides'.

8. The combination of the Water tank .El with one of more tanks for-holding the liquid deoxidizing or carbureting agents, for the purpose of applying the pressure of live steam or of ahead of water to forcing the deoxidizing agents intothe reducing-chamber, substantially .as h ereinbefore described.

' 9. Constructing the tuyere forming the com-l munication between the interior of the reducing-chamber and the cell below it of fire-clay 

